WO2008046831A1

WO2008046831A1 - Aqueous dispersions of silica for increasing early strength in cementitious preparations

Info

Publication number: WO2008046831A1
Application number: PCT/EP2007/061039
Authority: WO
Inventors: Ulrich Fischer; Philipp Wieland; Christian Hübsch; Harald Grassl; Kerstin Becher; Stefanie Scheul; Eva Jetzlsperger
Original assignee: Evonik Degussa Gmbh; Construction Research & Technology Gmbh
Priority date: 2006-10-20
Filing date: 2007-10-16
Publication date: 2008-04-24
Also published as: KR20090081373A; CN101568499B; US8835535B2; JP2010506987A; JP5268924B2; HUE031486T2; DE102006049524A1; PT2079670T; EP2079670B1; ES2599756T3; PL2079670T3; EP2079670A1; CN101568499A; KR101390555B1; US20100324173A1

Abstract

The invention relates to a dispersion which is free of binders and which contains silica and at least one flow agent, the silica being a precipitated silica having a surface area greater than 50 m²/g, the aggregates and/or agglomerates in the dispersion having an average diameter of less than 1 µm and the content of silica being 5 to 50% by weight, based on the total amount in the dispersion. The invention also relates to a method for producing the same and to its use as a concrete admixture in cementitous preparations.

Description

Aqueous dispersions of precipitated silicas and silicates to increase the early strength in cementitious

preparations

The invention relates to a dispersion based on silica and a flow agent, and their use as concrete admixtures.

Two essential criteria for the use of cementitious preparations are, on the one hand, their ability to be conveyed to the place of processing and, on the other hand, the duration to which this preparation attains a strength which permits further processing or processing. This duration is also described in the literature as early strength and is to be understood in the context of the present text as the strength of a cementitious preparation after <48 h of cement hydration.

It is known that the conveyance can be influenced by the addition of so-called flow agents (cf .. EP-A 214 412, DE-PS 16 71 017, US 5,707,445 Bl, EP 1 110 981 A2, EP 1 142 847 A2).

It has also been known for a long time, for example from US Pat. No. 3,135,617, that acceleration of the setting can be achieved by addition of a finely divided amorphous silicon dioxide to form cementitious preparations. However, this could not prevail because it greatly reduced the processability of the fresh concrete.

WO02 / 070429 discloses a composite material containing inorganic aggregates, ultrafine particles, a cementitious binder and a concrete plasticizer. The composite material allows the production of a highly liquefied concrete in which no bleeding occurs. As ultrafine particles become mainly Silica fume particles have a strong filler effect in cement or concrete compositions but are less reactive due to their low specific surface area. Alumina, fly ash, pozzolans, calcium carbonate, alumina, barium sulfate and titanium dioxide can be used as further particles of this size. The stated particles have the disadvantage that they have too low nucleation rates of the strength-forming phases and thus lead to low early strengths.

The proportion of the ultrafine particles, based on the total amount of the composite material, is 1 to 30% by weight or about 10 to 25% by weight in the exemplary embodiments, based on the sum of cement and ultrafine particles. Thus, the required proportion of ultrafine particles is very high.

In US6752866 there is disclosed a method of improving early strength by adding an aqueous dispersion containing a mineral filler and a specific dispersant to cement. Calcium carbonate, barium carbonate, limestone, dolomite, talc, silica, titanium dioxide, kieselguhr, iron oxide, manganese oxide, lime, kaolin, clay, mica, gypsum, fly ash, slag, calcium sulfate, zeolites, basalt, barium sulfate or aluminum trihydroxide can be used as mineral fillers. Preferably, calcium carbonate is used. The disclosed mean particle diameter of the mineral fillers used are in the range of about 2 to about 10 microns. Essential to the invention disclosed in US6752866 is a special dispersant. This contains a copolymer which by free radical copolymerization of a Alkoxypolyalkylenglykol urethanes with a anionic or nonionic monomer is obtained. No specific information is given on the required quantities of mineral filler, dispersant and cement. From the exemplary embodiments it can be seen that the proportion of mineral filler with 10 wt .-%

(Silica, test number 12) or 30% by weight

(Silica, test number 17) and the proportion of

Dispersant 0.5 (test number 17) or 0.75

Wt .-% (test number 12), based on silica, is. These dispersions show only a small amount

Stability to sedimentation.

WO01 / 90024 discloses a concrete composition containing aggregates, a hydraulic binder, silica sol and a polycarboxylate. The BET surface area of the silica sol is preferably 300 to 900 m ² / g. Silica sols are single particles with a diameter of 3 to 50 nm and only in dispersion resistant. In WO01 / 90024 nothing is disclosed about the influence of the described silica sol on the early strength. However, it is known to the person skilled in the art that in the case of silica sol concentrations in which a significant increase in the early strength is achieved, the processability is also significantly reduced, so that high amounts of flow agent are necessary. It is believed that this is because silica sols dissolve rapidly in the highly alkaline cement or concrete compositions. The silica sols are therefore available only to a small extent as a germ for the formation of the strength-forming calcium silicate hydrate phases available.

Wagner and Hauck show in Wiss. Z. Hochsch. Archit. Construction. Weimar 40 (1990), p.183, that the sequence of addition of the various constituents in the production of a concrete has a significant influence on the early strength and the flow requirements, if early strength-increasing oxides are used. In the Investigation, the oxide was added separately from the flow agent.

In the patent US 5030286 40-60% dispersions at pH 4-8.5 having an average particle diameter of 0.3 to 3 microns are described. The patent examples show that the dispersions are only stable if they are stirred at least slightly or dispersants are used for stabilization.

The patent US 6761867 calls dispersions having a mean particle size d ₅ o of less than 5 microns. The

However, patent examples only show dispersions whose average particle size is in the μm range. The

Deagglomeration occurs here at pH <4. Again, z. T. dispersants added. Furthermore, in the case of the dispersions according to US Pat. No. 6,761,867, a considerable increase in the viscosity is already determined after 10 days of storage.

The state of the art shows that there is a keen interest in developing concrete compositions which have a high early strength combined with good processability, without having to use large amounts of fluid. The prior art further shows that the currently available superplasticizers and particles in the cement or concrete composition constitute a sensitive system. For example, the order of addition and the concentration of starting materials have a decisive influence on the processability and early strength of the concrete.

The object of the invention is therefore to provide a concrete additive and a process for its preparation, with which the disadvantages of the prior art can be minimized. In particular, the concrete admixture should significantly increase the early strength of concretes with good processability. The invention relates to dispersions, a process for their preparation and their use as defined and described in the claims, the description and the examples of the present application.

The present invention in particular dispersions are characterized in that

they contain at least one precipitated silica and / or a silicate, and at least one flow agent,

- that at least one precipitated silica and / or a silicate has a BET surface area greater than 50 m ² / g,

- The aggregates and / or agglomerates of the precipitated silica and / or silicate in the dispersion have a mean diameter of less than 1 micron, and

- The proportion of silica from 5 to 50 wt .-%, based on the total amount of the dispersion is.

Another object of the invention is a process for the preparation of the dispersion according to the invention, in which

a) with stirring to an aqueous starting dispersion of silica in which the aggregates and / or agglomerates have a mean diameter of less than 1 micron and a BET surface area greater than 50 m ² / g, a flow agent in the form of a powder or as an aqueous solution of the solvent and optionally further diluted with water

or

b) dispersed a precipitated silica powder in an aqueous solution of a flow agent by means of a suitable dispersing aggregate and subsequently optionally further diluted with water or

c) dispersing the silica powder in an aqueous phase, preferably in water, and then adding the resulting dispersion to an aqueous solution of the flow agent. The mixing in of the dispersion can in this case take place under very low shear energy, for example by means of a propeller stirrer.

Another object of the invention is the use of the dispersion of the invention as concrete admixture.

Another object of the invention is a cementitious preparation containing the dispersion of the invention.

The proportion of silicon dioxide in the cementitious preparation is preferably from 0.01 to <2% by weight, based on the cement.

The novel dispersions are distinguished by the fact that the early strength of concrete is improved.

The dispersions of the invention combine silica and plasticizers in a single composition, eliminating mixing during the concrete preparation, resulting in a simplified and accelerated concrete formulation. Furthermore, this reduces the number of possible different sequences of addition in the production of concrete preparations, which leads to a simplification of the process and to a reduction of error sources.

It has also been found that the dispersions according to the invention have good storage stability. Without being bound to any particular theory, this very positive effect is due to a stabilizing interaction of the silica particles with the flow aid. In particular, the good storage stability allows the commercial use of the dispersions in the first place.

Finally, the use of the dispersions of the invention has the advantage of significantly better handling in comparison to the separate use of silica powders and flow agents. Compared to powder products, the freedom from dust is improved and the dosage is simplified. Furthermore, an improvement in the early strength of concrete was found by the dispersions of the invention compared to the use of the same powdered silica and the same superplasticizer, each separately.

In the present invention, the terms designate

Silica and silica particles the same substance. These include precipitated silicas and / or

Understood silicates. Particular preference is given to precipitated silicas.

The terms silicic acid, precipitated silica, precipitated silica and precipitated silica are used synonymously. In all cases, it includes precipitated silica, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A23, pages 642-647. To avoid mere repetition, the content of this document is hereby explicitly incorporated into the subject matter and the description of the present invention. Precipitated silica may have BET surface areas up to 800 m ² / g and is obtained by reacting at least one silicate, preferably an alkali and / or alkaline earth silicate, with at least one acidifier, preferably at least one mineral acid. In contrast to silica gels (see Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A23, pp. 629-635), precipitated silicas do not consist of a uniform three-dimensional SiO ₂ network but of individual ones Aggregates and agglomerates. A particular feature of precipitated silica is the high level of so-called internal surface, which is reflected in a very porous structure with micro- and mesopores.

Precipitated silicas differ from pyrogenic ones

Silicas, which are also referred to as aerosils

(See Ullmann's Encyclopedia of Industrial Chemistry, 5.

Edition, Vol. A23, pp. 635-642). Pyrogenic silicic acids are obtained by flame hydrolysis of silicon tetrachloride. Due to the completely different manufacturing process, fumed silicas have, inter alia, a different surface finish than precipitated silicas. This expresses z. In the lower number of silanol groups on the surface. The behavior of pyrogenic silicic acids and precipitated silicic acids and thus also their behavior in aqueous dispersions is mainly determined by the surface properties. Therefore, these can not be compared. Precipitated silicic acid white compared to Among other things, the advantage of pyrogenic silicic acids is that they are considerably less expensive.

Silicates are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A23, pp. 661-717. To avoid pure repetition, the content of this document is hereby explicitly incorporated in the subject matter and the description of the present invention.

Silica sols are to be understood as meaning particles according to Winnacker, Kuchler, 5th ed., Vol. 3, p. 868. In contrast to silica sols in which the silica particles are present as primary particles, the particles of the inventive silicic acid dispersions are secondary particles, ie aggregated primary particles. The dispersions according to the invention are preferably aqueous dispersions, ie, at least one constituent, particularly preferably the main constituent, of the liquid phase is water, preferably deionized water. In addition to water and at least one silica, dispersions according to the invention in the liquid phase additionally comprise at least one flow aid. In a particularly preferred embodiment, the dispersions according to the invention otherwise contain no further liquid additives, especially those which prevent the sedimentation of the silica particles.

The dispersions of the invention are preferably free of binders. In this case, binders are inorganic substances, such as cement, or organic substances to understand, which are processable in the plastic state, and harden in the course of a period of time birnir and thereby connect other substances together.

Furthermore, the dispersions of the invention are preferably free of inorganic dispersants and mechanical stabilizers, such as e.g. Latex.

It is also possible that the dispersion of the invention contains the precipitated silica as a single solid. This may be particularly useful if the dispersion is to serve as a masterbatch for various applications.

In the case of a precipitated silica, the BET surface area of the silica present in the dispersion according to the invention is preferably in the range from 50 to 800 m ² / g, preferably 50 to 500 m ² g, particularly preferably in the range from 100 to 400 m ² / g. and most preferably in the range of 150-250 m ² / g.

Preferably, the BET surface area of the silica present in the dispersion according to the invention is in the case of a silicate is in the range of 50-800 m ² / g, more preferably in the range of 50-500 m ² / g, most preferably in the range of 50-290 m ² / g, particularly preferably in the range of 70-250 m ² / g, and especially preferably 70-150 m ² / g.

If a plurality of silicas are present side by side in the dispersions of the invention, the BET surface area is based on the total surface area formed by the silicas. In this case, the BET is preferably in the range of in the range of 50-800 m ² / g, more preferably 50-500 m ² g, most preferably in the range of 70-500 m ² / g, and most preferably in the range of 70-250 m ² / g.

Due to the influence of the existing in comparison to silica sol inner surface and the enlarged compared to microsilica outer surface of the silicon dioxide contained in the dispersion of the invention, the early strength of the concrete preparations is significantly improved.

For the inventive dispersion, the following preferred ranges should be mentioned for the average diameter d ₅ o of the aggregates and / or agglomerates in the dispersion: from 50 to 900 nm is from 50 to 750 nm, from 100 to 500 nm and from 150 to 350 nm. Values below 50 nm are technically difficult to implement and have no advantages in the application. By reducing the mean particle size in comparison to prior art dispersions, the storage stability of the dispersions according to the invention is markedly improved. At the same time, this results in a greater number of individual particles being present in the same amount by weight of silica, so that more germs are available for forming the strength-forming calcium silicate hydrate phases and thus the early strength of concrete preparations is further improved. The proportion of precipitated silica in the dispersion of the invention is 5 to 50 wt .-%, based on the total amount of the dispersion. Dispersions according to the invention which have a silicon dioxide content of from 10 to 50% by weight, preferably from 20 to 40% by weight, particularly preferably from 20 to 35% by weight and very particularly preferably from 25 to 35% by weight usually better stability than higher filled dispersions. Dispersions containing less than 5% by weight of silica are not economical due to the high water content.

The dispersions according to the invention preferably have a pH of from 8 to 12, preferably from 8.5 to 10, more preferably from 8.8 to 10 and especially preferably from 9 to 10. It has been found that the pH of the dispersions should not be too low. The pH of the dispersions according to the invention has a particular stabilizing effect on the sedimentation properties of the dispersion.

The dispersion according to the invention contains at least one flow agent. Suitable flow agents may be: lignosulfonate, sulfonated naphthalene-formaldehyde polycondensates (cf EP0214412), sulfonated melamine-formaldehyde polycondensates (cf., DE1671017) and polycarboxylate ethers (cf., US5707445, EP1110981, EP1142847). The content of the cited patents is hereby incorporated explicitly into the content of the present application.

It is preferably a water-soluble Polxycarboxylatether in the form of a copolymer which is composed of polyoxyalkylene-containing structural units and carboxylic acid and / or carboxylic anhydride monomers and optionally other monomers. The weight ratio of flow agent / silicon dioxide in the dispersion according to the invention is from 0.01 to 100. This ratio may preferably be from 0.01 to 50, particularly preferably from 0.05 to 20, very particularly preferably from 0.01 to 10, in particular 0.05. 5, more preferably 0.1 to 1 and most preferably 0.1 to 0.5.

The dispersion of the invention may contain a copolymer having the components a), b), c), preferably with the components a), b), c), and d). The proportion of the assembly a) is 51 to 95 mol%, the assembly b) 1 to 48.9 mol%, the assembly c) 0.1 to 5 mol% and the assembly d) 0 to 47, 9 mol%.

The first component a) represents a mono- or dicarboxylic acid derivative having the general formula Ia, Ib or Ic.

COX

- CH ₂ - CR ¹ - - CH ₂ - C - - CH ₂ - C - CH ₂

COX CH ₂ O = CC = O

\ /

COX Y

Ib Ib

In the monocarboxylic acid derivative Ia R ^{1 is} hydrogen or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, preferably a methyl group. X in the structures Ia and Ib stands for - OM _a and / or - O - (C _m H _2m O) _n -R ² or -NH- (C _m H _2m O) _n -R ² with the following meaning for M , a, m, n and R ² :

M is hydrogen, a mono- or di-valent

Metal cation, ammonium, an organic amine residue and a = ^ or 1, depending on whether M is a on or divalent cation is. As organic amine radicals are preferably substituted ammonium groups which derive from primary, secondary or tertiary Ci- ₂ o ~ alkylamines, Ci ₂ o ~ alkanolamines, _C5 - ₈ - cycloalkylamines and Cs ₁₄ -Arylaminen. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.

R ² is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an aryl radical having 6 to 14 C atoms, which may optionally be substituted, m = 2 to 4 and n = 0 to 200 can be. The aliphatic hydrocarbons may hereby be linear or branched and saturated or unsaturated. Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, and the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups.

Instead of or in addition to the dicarboxylic acid derivative according to formula Ib, the subunit a) (mono- or dicarboxylic acid derivative) may also be present in cyclic form according to formula Ic, where Y = O (acid anhydride) or NR ² (acid imide) may represent above designated meaning for R ² .

The second module b) corresponds to formula II

- CH ₂ - CR -

(CH ₂ ) _p -O- (C _m H _2m O) _n -R ² and is derived from oxyalkylene glycol alkenyl ethers in which m, n and R ^{2 have} the meaning given above. R ³ in turn represents hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms, which may also be linear or branched or unsaturated, p may assume values between 0 and 3.

According to the preferred embodiments, in the formulas Ia, Ib and II, m = 2 and / or 3, so that they are polyalkylene oxide groups which are derived from polyethylene oxide and / or polypropylene oxide. In a further preferred embodiment, p in formula II is 0 or 1, d. H. they are vinyl and / or alkyl polyalkoxylates.

The third assembly c) corresponds to the formula IHa or IHb

R "FT FT

■ CH - C - - CH - CH CH - CH -

ST (CH ₂ ) _Z V (CH ₂ ) _Z purple INb

In formula IIIa, R ⁴ can be H or CH ₃ , depending on whether it is acrylic or methacrylic acid derivatives. In this case, S can be -H, -COOM _a or -COOR ⁵ , where a and M have the abovementioned meaning and R ^{5 is} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or Aryl radical having 6 to 14 carbon atoms can be. The aliphatic hydrocarbon radical may also be linear or branched, saturated or unsaturated. The preferred cycloaliphatic hydrocarbon radicals are in turn cyclopentyl or cyclohexyl radicals and the preferred aryl radicals phenyl or naphthyl radicals. In the case of T = -COOR ⁵ , S = COOM _a or -COOR ⁵ . In the event that T and S = COOR ⁵ , the corresponding assemblies are derived from the dicarboxylic acid esters.

In addition to these ester structural units, the assemblies c) may have other hydrophobic structural elements. These include the polypropylene oxide or polypropylene oxide-polyethylene oxide derivative with

T = - U ¹ - (CH - CH ₂ - O) _x - (CH ₂ - CH ₂ - O) _y - R ⁶

x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (polyethylene oxide) derivatives may hereby be linked via a grouping U ¹ to the ethyl radical of the group c) corresponding to formula IUa, where U ^{1 is} -CO-NH-, -O- or -CH ₂ -O- can. These are the corresponding amide, vinyl or allyl ethers of the assembly according to formula IIIa. R ⁶ here again can be R (meaning of R see above) or

where U = -NH-CO-, -O-, or -OCH ₂ - and S has the meaning described above. These compounds are polypropylene oxide (polyethylene oxide) derivatives of the bifunctional alkenyl compounds according to formula IUa. As a further hydrophobic structural element, the compounds corresponding to formula IUa may contain polydimethylsiloxane groups, which in the formula scheme IHa T = - W - R ⁷ corresponds.

W means here

(hereinafter referred to as polydimethylsiloxane grouping), R ⁷ kkaannnn == FR ² and r can assume values of 2 to 100 here.

The polydimethylsiloxane grouping can not only be bonded directly to the ethylene radical according to formula IUa, but also via the groupings

- CO - [NH- (CH ₂₎ _3] _s - W-R ⁷ or - CO - O (CH ₂₎ _Z - W -R ^7,

where R ^{7 is} preferably = R ² and s = 1 or 2 and z = 0 to 4. R ⁷ can also still

- [(CH ₂ ) ₃ - NH] ₈ - CO - C = CH or - (CH ₂ ) _Z - O - CO - C = CH

R ⁴ SR ⁴ S

These are the corresponding difunctional ethylene compounds corresponding to the formula IIIa, which are linked to one another via the corresponding amide or ester groups and where only one ethylene group has been copolymerized.

The situation is similar with the compounds of the formula IIIa where T = (CH ₂ ) _Z -V- (CH ₂ ) _Z -CH = CH-R ² , where z = 0 to 4, V is either a polydimethylsiloxane radical W or one - O-CO-C6H can be ₄ -CO-O-radical and R ,? has the meaning given above. These compounds are derived from the corresponding dialkenyl-phenyl-dicarboxylic acid esters or dialkenyl-polydimethylsiloxane derivatives.

It is also possible in the context of the present invention that not only one, but both ethylene groups of the difunctional ethylene compounds have been copolymerized. This essentially corresponds to the assemblies according to the formula IHb

FT FT

- CH - CH CH - CH -

(CH ₂ ) z V - (CH ₂ ) z

IIIb

wherein R, V and z have the meaning already described.

The fourth group d) is derived from an unsaturated dicarboxylic acid derivative of the general formula

IVa and / or IVb as defined above for a, M, X and Y.

-CH CH-CH CH

COOM ₃ COX ^ ^,

O Y O IVa IVb

The copolymers preferably contain 55 to 75 mol% of the structural groups of the formula Ia and / or Ib, 19.5 to 39.5 mol% Structural groups of the formula II, 0.5 to 2 mol% of structural groups of the formula IIIa and / or IIIb and 5 to 20 mol% of structural groups of the formula IVa and / or IVb.

According to a preferred embodiment, the copolymers according to the invention additionally contain up to 50 mol%, in particular up to 20 mol% based on the sum of the components a to d, structures based on monomers based on vinyl or (meth) acrylic acid -Derivaten such as styrene, methyl styrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, Methallylsulfonsäure, vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, allylhexyl acrylate, inter alia based.

The number of repeating structural units in the copolymers is not limited. However, it has proven to be particularly advantageous to set average molecular weights of from 1,000 to 100,000 g / mol.

The preparation of the copolymers can be carried out in various ways. It is essential here that 51 to 95 mol% of an unsaturated mono- or dicarboxylic acid derivative, 1 to 48.9 mol% of an oxyalkylene-alkenyl ether, 0.1 to 5

Mol% of a vinylic polyalkylene glycol, polysiloxane or ester compound and 0 to 55 mol% of a dicarboxylic acid derivative by means of a radical

Starters polymerized.

The unsaturated mono- or dicarboxylic acid derivatives which form the structural groups of the formulas Ia, Ib or Ic are preferably used: acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid imide and itaconic acid monoamide.

Instead of acrylic acid, methacrylic acid, itaconic acid and itaconic monoamide can also their mono- or divalent Metal salts, preferably sodium, potassium, calcium or ammonium salts are used.

As acrylic, methacrylic or itaconic acid esters especially derivatives are used, the alcoholic component of a polyalkylene glycol of the general formula HO- (C _m H _2m O) _n R ² with R ² = H, aliphatic hydrocarbon radical having 1 to 20 carbon atoms , cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, optionally substituted aryl radical having 6 to 14 carbon atoms and m = 2 to 4 and n = 0 to 200.

The preferred substituents on the aryl radical are -OH, -COO- or -SU ₃ groups.

The unsaturated monocarboxylic acid derivatives can only be present as monoesters, while diester derivatives are also possible in the case of the dicarboxylic acid itaconic acid.

The derivatives of the formulas Ia, Ib and Ic can also be present as a mixture of esterified and free acids and are used in an amount of preferably 55 to 75 mol%.

The second component for the preparation of the copolymers of the invention is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 19.5 to 39.5 mol%. In the preferred oxyalkylene glycol alkenyl ethers corresponding to the formula V

CH ₂ = CR ³ - (CH ₂ ) _P - O - (C _m H _2m O) _n - R ² V

R ³ = H or an aliphatic hydrocarbon radical having 1 to 5 C atoms and p = 0 to 3. R ² , m and n have the meaning already mentioned above. Particularly advantageous here is the use of polyethylene glycol monovinyl ether (p = 0 and m = 2) where n preferably has values between 1 and 50.

As a third component for introducing the assembly c) is preferably 0.5 to 2 mol% of a vinylic polyalkylene glycol, polysiloxane or ester compound used. As preferred vinylic polyalkylene glycol compound, derivatives corresponding to formula VI are used,

CH = C - R

SU ¹ - (CH - CH ₂ - O) _x - (CH ₂ - CH ₂ - O) _y - R ⁶ VI

wherein S may preferably be -H, or COOM _a and U ¹ = -CO-NH-, -O- or -CH ₂ O-, ie it is the acid amide, vinyl or allyl ethers of the corresponding polypropylene glycol or Polypropylene glycol-polyethylene glycol derivatives. The values for x are 1 to 150 and for y = 0 to 15. R ⁶ can either be R ¹ again or

- CH ₂ - CH - U ² - C = CH R ⁴ R ⁴ S

where U ² = -NH-CO-, -O- and -OCH ₂ - and S = -COOM _a and preferably -H.

In the case of R ⁶ = R ² and R ² preferably H is the polypropylene glycol (-Polyethylenglykol) -Monamide or

Ethers of the corresponding acrylic (S = H, R ⁴ = H), methacrylic (S = H, R ⁴ = CH ₃ ) or maleic acid (S = COOM _a , R ⁴ = H) -

Derivatives. Examples of such monomers are maleic acid N-

(methylpolypropylene glycol) monoamide, maleic acid N- (methoxy-polypropylene glycol-polyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ether.

In the case of R ⁶ ≠ R ² are bifunctional vinyl compounds whose polypropylene glycol (polyethylene glycol) derivatives via amide or ether groups (-O- or -OCH ₂ -) are interconnected. Examples of such compounds are polypropylene glycol bismaleamic acid, polypropylene glycol diacrylamide, polypropylene glycol dimethacrylamide, polypropylene glycol divinyl ether, polypropylene glycol dialkyl ether.

The preferred vinylic polysiloxane compound used are derivatives corresponding to formula VII,

R ⁴

CH ₂ = C VII WR ⁷

where R ⁴ = - H and CH ₃ ,

W

and r = 2 to 100 and R ^{7 is} preferably = R ¹ . Examples of such monomers are monovinylpolydimethylsiloxanes.

As further vinylic polysiloxane compound derivatives according to the formula VIII in question,

R ⁴

CH ₂ = C VIII

CO - [NH - (CH ₂ ) ₃ ] _S - W - R ⁷ where s = 1 or 2, R ⁴ and W have the abovementioned meaning and R ⁷ either = R ² or

- [(CH ₂ ) ₃ - NH] ₈ - CO - C = CH

R ⁴ S

may be and S is preferably hydrogen.

Examples of such monomers having a vinyl function (R ⁷ = R ² ) are polydimethylsiloxanepropylmaleamic acid or polydimethylsiloxanedipropyleneaminomaleamic acid. In the case of R ⁷ ≠ R ² are Divinylverbindungen such. B. polydimethylsiloxane bis (propylmaleinamidsäure) or polydimethylsiloxane bis (dipropylenaminomaleinamidsäure).

As a further vinylic polysiloxane compound is a preferred derivative according to the formula:

R ⁴

CH ₂ = C IX

CO - O - (CH ₂ ) _Z - W - R ⁷

where z can be 0 to 4 and R ⁴ or W have the abovementioned meaning. R ⁷ can either be R ² or else

- (CH ₂ ) _Z - O - CO - C = CH

R ⁴ S

be, where S is preferably hydrogen. Examples of such monovinylic compounds (R ⁷ = R ¹ ) are polydimethylsiloxane (1-propyl-3-acrylate) or polydimethylsiloxane (1-propyl-3-methacrylate).

In the case of R ⁷ ≠ R ² are Divinylverbindungen such. Polydimethylsiloxane bis (1-propyl-3-acrylate) or polydimethylsiloxane bis (1-propyl-3-methacrylate). As vinylic ester compound in the context of the present invention it is preferred to use derivatives corresponding to the formula X,

CH = CH

SC IOOR ^{5 χ}

where S = COOM _a or - COOR ⁵ and R ^{5 can be} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms and an aryl radical having 6 to 14 C atoms, a and M have the above meaning. Examples of such ester compounds are di-n-butylmaleinate or fumarate or mono-n-butylmaleinate or fumarate.

Furthermore, it is also possible to use compounds corresponding to formula XI

xi

where z can in turn be 0 to 4 and R ^{2 has} the already known meaning. V here can be W (ie a polydimethylsiloxane grouping), which corresponds to a dialkenylpolydimethylsiloxane compound such as divinylpolydimethylsiloxane. Alternatively, V can also be -O-CO-CeH ₄ -CO-O-. These compounds are dialkenylphthalic acid derivatives. A typical example of such phthalic acid derivatives is diallyl phthalate.

The molecular weights of the compounds which form the assembly c) can be varied within wide limits and are preferably between 150 and 10,000. As the fourth component for the preparation of the copolymers, it is preferable to use 5 to 20 mol% of an unsaturated dicarboxylic acid derivative (XII):

M _a OOC - CH = CH - COX XII

with the already given meaning for a, M and X.

For the case X = OM _a , the unsaturated dicarboxylic acid derivative is derived from maleic acid, fumaric acid, mono- or divalent metal salts of these dicarboxylic acids, such as the sodium, potassium, calcium or ammonium salt or salts with an organic amine radical. Additionally used monomers which form the unit Ia are polyalkylene glycol monoesters of the abovementioned acids having the general formula XIII:

M _a OOC - CH = CH - COO - (C _m H _2m O) _n - R

have, with the already given meaning for a, m, n and R ² .

The fourth component can also be derived from the unsaturated dicarboxylic anhydrides and imides of the general formula XIV (5 to 20 mol%)

CH = CH

/ \ O = C C = O XIV

with the meaning given above for Y.

According to the invention, according to a preferred embodiment, up to 50, preferably up to 20 MoI%, based on the sum of the components a) to d), can be used further monomers as described above.

The dispersion according to the invention can furthermore contain a copolymer whose base is an oxyalkenylglycol alkenyl ether and the copolymer contains the components a), b) and c). The proportion of the assembly a) is 10 to 90 mol%, the assembly b) 1 to 89 mol%, the assembly c) 0.1 to 5 mol% and the assembly d) 0.1 to 10 mol% %.

The first component a) represents an unsaturated dicarboxylic acid derivative corresponding to the formula IVa or IVb.

-CH CH-CH CH

COO ₃ M COX ^ ^.

O Y O

IVa IVb

For the dicarboxylic acid derivative corresponding to formula Id, M = hydrogen, a mono- or divalent metal cation, ammonium ion, an organic amine radical, and a = 1, or in the case where M is a divalent cation, 1/2. Then, together with a grouping likewise containing M _a with a = 1/2, a bridging over M occurs, which exists only theoretically as M _a with a = 1/2.

The monovalent or divalent metal cation is preferably sodium, potassium, calcium or magnesium ions. Substituted ammonium groups which are derived from primary, secondary or tertiary C ₁ - to C ₂ -alkylamines, C ₁ - to C ₂ -alkanolamines, C ₅ - to C 8 -cycloalkylamines and C 6 -to C ₄ -arylamines are preferably used as organic amine radicals , Examples of corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form. In addition, X also represents -OM _a or -Q- (C _1n H ₂ TOO) _n -R ¹ where R ¹ = H, an aliphatic one Hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms, which may still be substituted, m = 2 to 4 and n = 0 to 200 be can. The aliphatic hydrocarbon radicals may hereby be linear or branched as well as saturated or unsaturated.

Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, and the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups. Alternatively, X may be -NHR ² and / or - NR ² ₂ , which corresponds to the mono- or disubstituted monoamides of the corresponding unsaturated dicarboxylic acid, where R ^{2 may} in turn be identical to R ¹ or instead may be -CO-NH ₂ .

Instead of the dicarboxylic acid derivative corresponding to formula IVa, the assembly a) (dicarboxylic acid derivative) may also be present in cyclic form corresponding to the formula IVb, where Y = O (= acid anhydride) or NR ² (acid imide) and R ^{2 is} the one described above Has meaning.

In the second assembly according to formula II,

- CH ₂ - CR ^J -

Il (CH ₂ ) _P - O - (C _m H _2m O) _n - R ¹

which is derived from the oxyalkylene glycol alkenyl ethers, R ^{3 is} in turn hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms (which may also be linear or branched or unsaturated). p can assume values between 0 and 3 and R ² , m and n have the abovementioned meaning. According to one preferred embodiment in formula H p = O and m = 2 or 3, so that they are assemblies derived from the polyethylene oxide or polypropylene oxide vinyl ether.

The third assembly c) corresponds to the formula IHa or IHb

R "R 'R ^

■ CH - C - - CH - CH CH - CH -

ST (CH ₂ ) _Z V (CH ₂ ) _Z purple INb

In formula IIIa R ⁴ can be H or CH ₃ , depending on whether it is acrylic or methacrylic acid derivatives. Here S can be -H, COOM _a or -COOR ⁵ , where a and M have the abovementioned meaning and R ^{5 is} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an aryl radical with 6 to 14 carbon atoms can be. The aliphatic hydrocarbon radical may also be linear or branched, saturated or unsaturated. The preferred cycloaliphatic hydrocarbon radicals are again cyclopentyl or cyclohexyl radicals and the preferred aryl radicals are phenyl or naphthyl radicals. In the case of T = -COOR ⁵ , S = COOM _a or -COOR ⁵ . In the event that T and S = COOR ⁵ , the corresponding assemblies are derived from the dicarboxylic acid esters.

In addition to these ester structural units, the assemblies c) may have other hydrophobic structural elements. These include the polypropylene oxide or polypropylene oxide polyethylene oxide derivatives with T = - U ¹ - (CH - CH ₂ - O) _x - (CH ₂ - CH ₂ - O) _y - R ⁶

CH ₃

x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (polyethylene oxide) derivatives may be linked here via a grouping U ¹ with the ethyl radical of the group c) corresponding to formula IIIa, where U ^{1 is} -CO-NH-, -O- or -CH ₂ -O- can. These are the corresponding amide, vinyl or allyl ethers of the assemblies corresponding to formula IIIa. R ⁶ here again can be R ¹ (meaning of R ¹ see above) or

where U = -NH-CO-, -O- or -OCH ₂ - and S has the meaning described above. These compounds are polypropylene oxide (polyethylene oxide) derivatives of the bifunctional alkenyl compounds corresponding to formula IIIa.

As a further hydrophobic structural element, the compounds corresponding to formula IIIa may contain polydimethylsiloxane groups, which in the formula scheme IUa corresponds to T = -WR ⁷ .

W means here

(hereinafter referred to as polydimethylsiloxane grouping), R ⁷ can be = R ¹ and r can here assume values of 2 to 100. The polydimethylsiloxane group W can not only be bonded directly to the ethylene radical of the formula IUa, but also via the groupings

- CO - [NH- (CH ₂ ) ₃ ] _S - W - R ⁷ or - CO - O (CH ₂ ) _Z - W - R ⁷ ,

where R ^{7 is} preferably = R ¹ and s = 1 or 2 and z = 0 to 4.

R ⁷ can also still

- [(CH ₂ ) ₃ - NH] ₈ - CO - C = CH or - (CH ₂ ) _Z - O - CO - C = CH

.4 .4

- _| nr \ ö r \ ö

be. These are the corresponding difunctional ethylene compounds corresponding to the formula IIIa, which are linked to one another via the corresponding amide or ester groups and where only one ethylene group has been copolymerized.

The situation is similar with the compounds of the formula IIIa where T = - (CH ₂ ) _Z -V- (CH ₂ ) _Z -CH = CH-R ¹ , where z = 0 to 4, V is either a polydimethylsiloxane radical W or - may be an O-CO-C6H ₄ -CO-O radical and R ^{1 has} the meaning given above. These compounds are derived from the corresponding dialkenyl-phenyl-dicarboxylic acid esters or dialkenyl-polydimethylsiloxane derivatives.

It is also possible within the scope of the present invention that not only one, but both ethylene groups of the difunctional ethylene compounds have been copolymerized. This essentially corresponds to the assemblies according to the formula IHb R ¹ R ¹

- CH - CH CH - CH -

(CH ₂ ) z V (CH ₂ ) _Z

IIIb

wherein R ¹ , V and z have the meaning already described.

Preferably, these copolymers consist of 40 to 55 mol% of groups of the formula IVa and / or IVb, 40 to 55 mol%

Assembly of the formula II and 1 to 5 mol% of the assemblies

Formula IHa or IHb. According to a preferred

Embodiment, the copolymers additionally contain up to 50 mol%, in particular up to 20 mol%, based on the sum of the components a), b) and c), assemblies whose

Monomer is a vinyl, acrylic acid or methacrylic acid derivative.

The monomeric vinyl derivatives may preferably be derived from a compound selected from the group consisting of styrene, ethylene, propylene, isobutene or vinyl acetate. As a preferred monomeric acrylic acid derivative, the additional components are derived in particular from acrylic acid or methyl acrylate. Preferred monomeric methacrylic acid derivative is methacrylic acid, methyl methacrylate and hydroxyethyl methacrylate.

The number of repeating structural elements of the copolymers is not limited, but it has proved to be particularly advantageous to adjust the number of structural elements so that the copolymers have an average molecular weight of 1000 to 200,000.

The second component of the copolymers is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 40 to 55 mol%. Both preferred oxyalkylene glycol alkenyl ethers corresponding to the formula V

CH2 ⁼ CR - (CH2) p ^~ O ^~ (C _m H2m0) n ^~ R

V

R = H or an aliphatic hydrocarbon radical having 1 to 5 C atoms and p = 0 to 3. R ¹ , m and n have the meaning already mentioned above. In this case, the use of polyethylene glycol monovinyl ether (p = 0 and m = 2) has proven particularly advantageous, n preferably having values between 2 and 15.

The third component essential to the invention for introducing the components c) is preferably 1 to 5 mol% of a vinylic polyalkylene glycol, polysiloxane or ester compound. As preferred vinylic polyalkylene glycol compound, derivatives corresponding to formula VI are used,

CH = CR ⁴

U ¹ - (CH-CH ₂ -O) _x - (CH ₂ -CH ₂ -O) _y -R ^€

CH ₃

VI

where S may preferably be -H or COOM _a and U ¹ = -CO-NH-, -O- or -CH ₂ O-, ie it is the acid amide, vinyl or allyl ethers of the corresponding polypropylene glycol or polypropylene glycol Polyethylene glycol derivatives. The values for x are 1 to 150 and for y = 0 to 15. R ⁶ can either be R ¹ again or

-CH ₂ -C (JHH-U _T 2-C = CH

R ⁴ R ⁴ S

where U ² = -NH-CO-, -O- and -OCH ₂ - and S = -COOM _a and preferably -H.

In the case of R ⁶ = R ¹ and R ¹ is preferably H, there are the polypropylene glycol (-polyethylene glycol) monoamides or ethers of the corresponding acrylic (S = H, R ⁴ = H), methacrylic (S = H, R ⁴ = CH ₃ ) or maleic acid (S = COOM _a , R ⁴ = H) - derivatives. Examples of such monomers are maleic acid N- (methylpolypropylene glycol) monoamide, maleic acid N- (methoxy-polypropylene glycol-polyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ether.

In the case of R ⁶ φ R ¹ are bifunctional vinyl compounds whose Polvpropylenglykol- (polyethylene glycol) derivatives via amide or ether groups (-O- or -OCH ₂ -) are interconnected. Examples of such compounds are polypropylene glycol bismaleamic acid, polypropylene glycol diacrylamide,

Propylene glycol dimethacrylamide, polypropylene glycol divinyl ether, polypropylene glycol dialkyl ether.

R ⁴

CH ₂ = C

WR ⁷

VII where R ⁴ = -H and CH ₃ ,

W =

R ⁴

VIII

where s = 1 or 2, R ⁴ and W have the abovementioned meaning and R ⁷ can be either = R ¹ or else and S is preferably hydrogen.

f (CH ₂ ) ₃ -N ^~ ] jϊ-CO-C = CH

L / i i

R ⁴ S

Examples of such monomers having a vinyl function (R ⁷ = R ¹ ) are polydimethylsiloxanepropylmaleamic acid or polydimethylsiloxanedipropyleneaminomaleamic acid. In the case of R ⁷ ≠ R ¹ are divinyl compounds such as polydimethylsiloxane bis (propylmaleinamidsäure) or polydimethylsiloxane bis (dipropylenaminomaleinamidsäure).

As a further vinylic polysiloxane compound is a preferred derivative corresponding to the formula IX in question, CH ₂ = C

CO-O- (CH ₂ ) z -WR 'IX

where z can be 0 to 4 and R ⁴ or W have the abovementioned meaning. R ⁷ can either be R ¹ or else

-CH ₂ ) _z -O-CO-C = CH

R ⁴ S

be, where S is preferably hydrogen. Examples of such monovinylic compounds (RR ¹ ) are polydimethylsiloxane (1-propyl-3-acrylate) or polydimethylsiloxane (1-propyl-3-methacrylate;

In the case of R ≠ R is

Divinyl compounds, e.g. Polydimethylsiloxane bis (1-propyl-3-acrylate) or polydimethylsiloxane bis (1-propyl-3-methacrylate).

As vinylic ester compound in the context of the present

Invention are preferably used derivatives according to the formula X,

CH = CH

S COOR ⁵

X

where S = COOM _a or -COOR ⁵ and R ^{5 can be} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms and an aryl radical having 6 to 14 C atoms, a and M have the above meaning. examples for such ester compounds are di-n-butyl maleate or fumarate or mono-n-butyl maleate or fumarate.

Furthermore, it is also possible to use compounds corresponding to formula XI,

CH = CH CH = CH

I l I l

R ¹ (CH ₂ ) _Z -V- (CH ₂ ) _z - (CH ₂ ) _z R ¹

XI

where z can in turn be 0 to 4 and R ^{1 has} the already known meaning. Here, V can be W (ie a polydimethylsiloxane grouping), which is a dialkenylpolydimethylsiloxane compound, such as. B. Divinylpolydimethylsiloxane corresponds. Alternatively, V can also be -O-CO-C ₆ H ₄ -CO-O-. These compounds are dialkenylphthalic acid derivatives. A typical example of such phthalic acid derivatives is diallyl phthalate.

The molecular weights of the compounds which form the assembly c) can be varied within wide limits and are preferably between 150 and 10,000.

Furthermore, up to 50 mol%, in particular up to 20 mol%, based on the monomers with the components according to the formulas II, III and IV of a vinyl, acrylic or methacrylic acid derivative can be polymerized. The monomeric vinyl derivative used is preferably styrene, ethylene, propylene, isobutene or vinyl acetate, acrylic acid or methyl acrylate is preferably used as the monomeric acrylic acid derivative, while methacrylic acid methacrylic acid derivatives are preferably used in preference to methacrylic acid methacrylate and hydroxyethyl methacrylate.

The aforementioned copolymers are disclosed in EP-A-736553. The dispersion of the invention may further comprise a copolymer whose base is an oxyalkenylglycol (meth) acrylic ester and the copolymer contains the following components:

5-98 wt .-% of a monomer of the type (a) (alkoxy) polyalkylene glycol mono (meth) acrylic ester of the general formula XV

CH ₂ = C - R ¹ I

COO (R ² O) _m R ³

XV

wherein

R ^{1 represents} a hydrogen atom or the methyl group,

R ² O represents a genus or a mixture of two or more genera of an oxyalkylene group having 2-4 carbon atoms, with the proviso that two or more genera of the mixture may be added either in the form of a block or in random form,

R ^{3 is} a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and

m is a value which is the average number of moles of oxyalkylene groups, m being an integer in the range of 1 to 200. 95 to 2 wt .-% of a monomer of the (meth) acrylic acid type (b) of the general formula XVI

CH ₂ = C - R ⁴

COOM ¹

XVI

wherein

R ^{4 represents} a hydrogen atom or the methyl group, and M ^{1 represents} a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group or an organic amine group,

and 0 to 50% by weight of another monomer (c) which is copolymerisable with these monomers, with

Provided that the total amount of (a), (b) and (c) is 100% by weight.

Typical monomers (a) are:

Hydroxyethyl (meth) acrylate,

Hydroxypropyl (meth) acrylate,

Polyethylene glycol mono (meth) acrylate,

Polypropylene glycol mono (meth) acrylate,

Polybutylene glycol mono (meth) acrylate,

Polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polybutylene glycol mono (meth) acrylate,

Polypropylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate,

Methoxypolyethylene glycol mono (meth) acrylate, Methoxypolypropylene glycol mono (meth) acrylate,

Methoxypolybutylene glycol mono (meth) acrylate,

Methoxypolethylenglykolpolypropylenglykol mono (meth) acrylate,

Methoxypolyethylenglykolpolybutylenglykol

mono (meth) acrylate,

Methoxypolypropylene glycol polybutylene glycol mono (meth) acrylate,

Methoxypolyethylene glycolpolypropylene glycolpolybutylene glycol mono (meth) acrylate,

Ethoxypolyethylene glycol mono (meth) acrylate,

Ethoxypolypropylene glycol mono (meth) acrylate,

Ethoxypolybutylene glycol mono (meth) acrylate,

Ethoxypolyethylenglykolpolypropylenglykol

mono (meth) acrylate,

Ethoxypolyethylene glycol polybutylene glycol mono (meth) acrylate,

Ethoxypolypropylenglykolpolybutylenglykolmono (meth) acrylate and / or

Ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate.

Typical monomers (b) are: acrylic acid and methacrylic acid, mono- and divalent metal salts, ammonium salts and / or organic amine salts thereof.

Typical monomers (c) are: esters of aliphatic alcohols having 1 to 20 carbon atoms with (meth) acrylic acid; unsaturated

Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mono- and divalent metal salts, ammonium salts and / or organic amine salts thereof; Mono- or diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid,

Citraconic acid with aliphatic alcohols of 1 to 20 carbon atoms, with glycols of 2 to 4 carbon atoms, with

(Alkoxy) polyalkylene glycols from 2 to 100 addition of the above-mentioned glycols; unsaturated amides like

(Meth) acrylamide and (meth) acrylalkylamide; Vinyl esters like

Vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene; unsaturated sulfonic acids, such as (meth) allylsulfonic acid, sulfoethyl (meth) acrylate,

2-methylpropanesulfonic acid (meth) acrylamide,

Styrenesulfonic acid, mono- and divalent metal salts,

Ammonium salts and / or organic amine salts thereof.

The dispersions of the invention can be prepared by a process in which

or

b) dispersed a precipitated silica powder in an aqueous solution of a flow agent by means of a suitable dispersing aggregate and subsequently optionally further diluted with water

or

c) the silica powder in an aqueous phase, preferably in water, dispersed and then the resulting dispersion to an aqueous solution of Plasticizer gives. The mixing in of the dispersion can in this case take place under very low shear energy, for example by means of a propeller stirrer.

Preferably, a polycarboxylate ether is used as a flow agent for the preparation of the dispersions.

For the preparation of the o. G. Steps a) to c) used it may be advantageous to first prepare a predispersion. In a preferred embodiment, silica particles are dispersed in a liquid component, preferably water, more preferably deionized water. But it is also possible to redisperse a filter cake, d. H. Do not dry the silica particles first. This second embodiment is of course with economic advantages compared. connected to the first embodiment. Any hybrid forms of these two embodiments are also possible, d. H. it is possible to redisperse a filter cake and then add dried silica and vice versa. It is also possible to prepare base dispersions of mixtures of at least two different silicas.

The preparation of the predispersions is carried out in a manner known per se by means of suitable dispersing aggregates. Thus, the dispersion of the silica powder can be carried out in apparatuses which introduce a comparatively low shear energy into the system (e.g., dissolvers, rotor-stator systems). However, it is also possible to use the same aggregates which are used to produce the actual dispersion.

The pH of the predispersion or of the dispersion can, in an optional further step, be adjusted to the desired value, ie a value of 8.0 to 12, particularly preferably 8.5 to 12, very particularly preferably 8.7 to 10 and 9 to 9.5 are particularly preferably set. Depending on the pH of the silica, this can be done by adding a basic component or an acidifier. In principle, any basic agent can be used, preferably an alkali metal or alkaline earth metal hydroxide or organic bases or ammonia. In principle, any acidic agent can be used as acidulant, for. As mineral acids, organic acids.

According to a variant of the method, it is also possible to use silica whose pH has already been adjusted so that the silica itself adjusts the pH of the dispersion to the desired value. In this variant, the pH of the silica can be adjusted in one of the steps of preparing the silica, for example during precipitation or during drying, by adding suitable basic or acidic agents. In this regard, techniques known to those skilled in the art are known.

To prepare the dispersion, the silica to be dispersed and brought into contact with the liquid phase or the predispersion, whose pH has optionally been adjusted accordingly, are comminuted by means of a suitable aggregate.

In principle, any suitable dispersing aggregate can be used. So z. B. Dispergieraggregate suitable whose energy input is sufficient, the

To disperse silica powder or the filter cake so that the agglomerates after dispersion have a mean particle size of less than 1 micron. Depending on the solids, specific energy inputs of between 0.1 and 10 kWh / kg are required. To this high specific

Realizing energy entries can basically

Method with high power density and lower

Residence time, methods with low power density and high residence time and intermediate forms can be used. High-pressure systems such as Nanomizer, Microfluidizer and other nozzle systems, in which the dispersion flows through a nozzle under high pressure of up to 50 to 5000 bar and is dispersed by the energy dissipation in and after the nozzle, achieve very high energy inputs of already 5,000 kJ in a single passage / m ³ to 500,000 kJ / m ³ . Agitator mills, on the other hand, lead to significantly lower specific energy inputs per passage of 5 to 500 kJ / m ³ . In order to achieve sufficient particle fineness, the dispersion must pass through the mill much more frequently, which leads to significantly higher stress frequencies than in high-pressure systems. The high frequency of use at low intensity has a positive effect on the structure and the surface of the particles and thus the stability of the dispersion.

In order to achieve high filling levels and to obtain a stable dispersion with low viscosity, shearing energies of> 1000 kJ / m ³ should advantageously be applied. Particularly good results are achieved with agitator ball mills, high-pressure homogenizers or planetary ball mills. The operation of these mills is known to the person skilled in the art.

Particularly advantageous proved the use of ball mills, in particular stirred ball mills. The product flow through the mill can be done in pendulum or in circulation mode. Due to high circulation numbers, an arrangement in circulation mode is easier to realize here. The circulation rate can vary from 10 to 300 kg / h and is advantageously in the range from 25 to 200 kg / h, more preferably in the range from 50 to 150 kg / h and particularly preferably in the range from 80 to 120 kg / h. The agitator may be in the form of disks, pins, pin-to-pin arrangements, an annular gap, or the like. A disk arrangement is preferred. The grinding time depends on the dispersibility of the product and the amount used for 10 minutes to 80 hours, preferably 0.5 to 50 hours, more preferably 1 to 25 hours and particularly preferably 5 to 15 hours. As a result, specific energy inputs (based on kg dispersion) of 0.01 to 10 kWh / kg can be achieved. Preferably, energy inputs of 0.05 to 5 kWh / kg, more preferably 0.1 to 1 kWh / kg, very particularly preferably 0.1 to 0.5 kWh / kg and particularly preferably 0.25 to 0.3 kWh / kg , The grinding media may consist of glass, aluminum oxide, zirconium oxide or other inorganic oxides as well as various mixtures of inorganic oxides. Due to the high density, it is advantageous to use zirconium oxide grinding bodies which are stabilized against abrasion by means of yttrium oxide. The size of the grinding media can vary from 20 μm to a few mm, advantageously grinding bodies of the size from 0.02 to 10 mm, particularly preferably from 0.05 to 5 mm, very particularly preferably from 0.1 to 1 mm and particularly preferably from 0.2 to 0, 4 mm used. The Mahlkörperfüllgrad, based on the free volume of the grinding chamber can vary from 60 to 99%, preferably 70 to 95%, more preferably 80 to 95% and most preferably 90 to 95%. The peripheral speed of the grinding tool can vary from 1 m / s to 15 m / s, preferably 5 m / s to 15 m / s, more preferably 8 m / s to 12 m / s.

After grinding, the dispersion is optionally concentrated to the desired silica content. This concentration can be carried out by any technique known in the art, for example by reduction of the liquid medium such. B. by vacuum evaporation, cross-flow filtration, continuous or discontinuous centrifugation, filtration, or by increasing the solids content.

If low fill levels are to be achieved, the dispersion of the silica powder can also be carried out in apparatuses which introduce a comparatively low shear energy into the system (for example dissolvers, rotor-stator systems).

Determination of the particle size distribution

The determination of the particle distribution of the dispersions of the invention is carried out according to the principle of laser diffraction on a laser diffractometer (Horiba, LA-920). The particle distribution corresponds to the particle distribution of all particles present in the dispersion.

First, a sample of the silica dispersion is removed with stirring, transferred to a beaker and diluted by the addition of water without the addition of dispersing additives so that a dispersion having a weight fraction of about 1 wt .-% SiÜ2 is formed. Immediately following the dispersion, the particle size distribution is determined from a partial sample of the dispersion with the laser diffractometer (Horiba LA-920 with standard software). For the measurement a relative refractive index of 1.09 has to be chosen.

All measurements are carried out at 23 ⁰ C. The particle size distribution and the relevant variables such. B. the average particle size d ₅ o are automatically calculated by the device and displayed graphically. The instructions in the operating instructions must be observed. Determination of the BET surface area

If the silica is not present as a solid but in aqueous dispersion, the following sample preparation must be carried out before the BET surface area is determined:

100 ml of the silica dispersion are removed with stirring, transferred to a porcelain dish and dried for 72 h at 105 ⁰ C. To remove organic components, the dried silica is heated to 500 ^° C. for 24 h. After the silica sample has cooled, it is comminuted with a spatula and the BET surface area determined.

The BET surface area of silica as a solid is determined according to ISO 5794-1 / Annex D with the TRISTAR 3000 device (Micromeritics) after the multipoint determination in accordance with DIN ISP 9277.

Determination of the pH of the dispersion

The pH of the aqueous dispersions is based on DIN EN ISO 787-9 at 20 ⁰ C. To determine the pH, the dispersions are diluted with water to a weight fraction of 5% SiO 2.

Determination of DBP recording

The DBP absorption (DBP number), which is a measure of the absorbency of the precipitated silica, is determined on the basis of the DIN 53601 standard as follows:

12.50 g powdery or spherical silica with 0 - 10% moisture content (if necessary, the moisture content is set by drying at 105 ⁰ C in a drying oven) are in the kneader chamber (Article number 279061) of the Brabender Absorptometer ^ΛΛ E ^ΛΛ given (without damping of Output filter of the torque transducer). With constant mixing (rotary speed of the kneader blades 125 rpm), dibutyl phthalate is added dropwise at room temperature through the "Dosimaten Brabender T 90/50" dibutyl phthalate into the mixture at a rate of 4 ml / min Towards the end of the determination, the mixture becomes pasty as indicated by a steep increase in power demand, and when 600 digits (torque of 0.6Nm) are displayed, an electrical contact will cause both kneader and DBP dosing The synchronous motor for the DBP supply is coupled to a digital counter, so that the consumption of DBP in ml can be read.

The DBP recording is given in g / (100 g) and calculated using the following formula:

D _{Bp =} _V ^v * ^ D_ * 1w00 "* _ ^ 2_ _{+ κ}

E 100 g

With

DBP = DBP recording in g / (100 g)

V = consumption of DBP in ml

D = density of DBP in g / ml (1.047 g / ml at 20 ⁰ C)

E = weight of silica in g

K = correction value according to humidity correction table in g / (100 g)

The DBP uptake is defined for anhydrous, dried silica. If moist precipitated silicas are used, the correction value K must be taken into account for calculating the DBP absorption. This value can be determined from the following correction table, eg. For example, a water content of the silica of 5.8% would mean a 33 g / (100 g) addition for DBP uptake. The moisture content of the silicic acid is determined according to the method "Determination of moisture or loss of drying".

Moisture correction table for dibutyl phthalate uptake (anhydrous)

Determination of the moisture or the loss of drying

The moisture of silica is determined according to ISO 787-2 after drying for 2 hours in a convection oven at 105 0C. This drying loss consists predominantly of water moisture. Determination of the loss on ignition

According to this method of weight loss of silica based on DIN EN ISO 3262-1 at 1000 ⁰ C is determined. At this temperature escapes physically and chemically bound water as well as other volatile

Ingredients. The moisture content (TV) of the tested sample is determined according to the previously described method "Determination of moisture or dry loss" according to DIN EN ISO 787-2.

Determination of Al and Na content

The determination of the Al content is carried out as Al2O3, the Na content as Na2θ. Both determinations are carried out according to ISO 3262-18 by means of flame atomic adsorption spectroscopy.

Determination of SLO ₂ content

The determination of the SiO ₂ content is carried out according to ISO 3262-19.

Examples 1 - 3

Preparation of the dispersions

The characteristics of the silicas used for the preparation of the dispersions are given in Table 1.

The dispersions are prepared in a stirred ball mill (LME 4, Netzsch). The grinding chamber and the disc agitator are made of abrasion-resistant ceramic (AI ₂ O ₃ or ZrÜ 2) • The grinding balls of yttrium-stabilized ZrÜ 2 have a diameter of 0.2 to 0.4 mm and fill the grinding chamber to 90% (8.84 kg). For predispersion, 22.5 kg of deionized water are placed in a 501 container Bottom outlet submitted. Then 2.5 kg of silica are gradually stirred in by means of a dissolver disk (speed = 380-940 rpm, peripheral speed = 3-7.4 m / s) until the silica is dispersed in the liquid. Subsequently, the pH of the dispersion is adjusted to 9 with KOH. The pH is checked regularly and readjusted if necessary. To achieve the desired fineness, the dispersion is circulated through the ball mill. In all tests, the peripheral speed remains constant at 10 m / s and the throughput at approximately 100 kg / h.

By adding portions of additional silica in the receiving container, the concentration of the dispersion of SiC> 2 is further increased. The mill is still operated here in the cycle. When the desired SiO ₂ concentration has been reached, the dispersion is transferred to a container and the flow agent (polycarboxylate ether (PCE) according to EP-A-1189955, Example 2) in the form of an aqueous solution (PCE content = 45% by weight). %) at room temperature. The ratio of PCE to silica is adjusted according to Table 2.

The composition of the dispersions is shown in Table 2. The comparative example contains no silica but only PCE and is not a dispersion.

The dispersions according to the invention show, within a period of 6 months, no appreciable change with regard to sedimentation stability and viscosity.

Table 1

Ul K>

Table 2

Example 4: Technical Testing

The production of standard mortar as well as the testing of the strength takes place according to DIN EN 196-1. For the production of the mortar cement with the name CEM I 52.5 Mergelstetten is used. The mortar is produced at 20 ^° C. The mortar mixtures are admixed with the dispersions corresponding to a silicon dioxide content of 0.5% by weight, based on the weight of the cement. The water / cement ratio is always 0.4.

From the mortar according to DIN 196-1 test specimens of size 40 mm x 40 mm x 160 mm are produced. Based on this standard, the determination of the flexural strength and compressive strength after 8 h of aging of the test specimens is carried out on these test specimens.

The results are summarized in Table 3.

Table 3: Strength development of mortar prisms in

Presence of various dispersions of precipitated silicas

(Dosage in each case 0.5%, based on the cement weight);

Ratio water / cement = 0.4; FM = initial flow rate; BZF =

Bending tensile strength in N / mm ² ; DF = compressive strength in N / mm ²

The results obtained show a marked increase in the early strength (measured as flexural tensile strength after 8 h and compressive strength after 8 h) when using the dispersions according to the invention. It is also interesting that the dispersion 2 is more effective than the identical silica in dry form.

Furthermore, tests are carried out in the calorimeter. The cement used is CEM I 42.5 Bernburg. The dispersions of the invention used are Example 1 to Example 3. The dispersions are metered so that the proportion of silicon dioxide 0.5 wt .-% based on the cement used. The water / cement ratio is constant at 0.5. The comparison is made against Comparative Example 1, which contains no silica, but PCE. In all experiments, the initial flow was 24 +/- learning.

The curves obtained (FIG. 1) show the released energy in [mW / g CEM] versus time in [h] in the cement paste specimen. The heat development is due to the exothermic reaction of the silicate phases in the cement with water. The maximum of the curve obtained by calorimetry can be correlated with the strength development in the cement, i. a maximum occurring earlier means early development of early strength in the component.

The position of the maxima of the curves from FIG. 1 on the time axis are summarized in Table 4 below:

Table 4 From the results it can be concluded that the use of the dispersions according to the invention causes a significant acceleration of the cement hydration. The beginning of the silicate hydration and the maximum of the heat development are 8-12% earlier than in the case of Comparative Example 1.

Claims

Claims:

1. dispersion,

characterized in that

at least one precipitated silica and / or a silicate, and at least one flow agent is contained,

having at least one precipitated silica and / or silicate, a BET surface area greater than 50 m ² / g,

2. Dispersion according to claim 1, characterized in that the dispersion is free of binders.

3. Dispersion according to claim 1 or 2, characterized in that the aggregates and / or agglomerates in the dispersion have an average diameter of 50 to 750 nm.

4. Dispersion according to one of claims 1 to 3, characterized in that the proportion of silica in the

Dispersion in total 10 to 50 wt .-%, based on the total amount of the dispersion is.

5. Dispersion according to one of claims 1 to 4, characterized in that the weight ratio flow agent / silica 0.01 - 100.

6. Dispersion according to one of claims 1 to 5, characterized in that the pH of the dispersion is between 8 and 12.

7. Dispersion according to one of claims 1 to 6, characterized in that the flow agent is a water-soluble polycarboxylate ether.

8. Dispersion according to one of claims 1 to 7, characterized in that the polycarboxylate is a copolymer based on oxyalkenylglycol-alkenyl ethers and the copolymer contains the following components:

a) 51 to 95 mol% of the groups of the formula Ia and / or Ib and / or Ic

COX

- CH ₂ - CR - - CH ₂ - C - - CH ₂ - C - CH ₂

COX CH ₂ O = CC = O

I \ /

COX Y

Ib Ib

in which

R ¹ = hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms

X = -0M _a , -O- (C _m H _2m O) _n -R ² , -NH- (C _m H _2m O) _n -R ²

M = hydrogen, a monovalent or divalent metal cation, ammonium ion, an organic amine radical,

a = ^ or 1

R = hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms

Y = O, NR ²

m = 2 to 4 and n = 0 to 200, b) 1 to 48.9 mol% of the general formula II

- CH ₂ - CR ³ -

(CH ₂ ) _p -O- (C _m H _2m O) _n -R ²

in which

R ^{3 is} hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms

p stands for 0 to 3 and

R, m and n have the abovementioned meaning,

c) 0.1 to 5 mol% of the groups of the formula IHa or IHb

R ⁴ R ² R ²

- CH - C - - CH - CH CH - CH -

ST (CH ₂ ) _Z V (CH ₂ ) _Z purple INb

where S = -H, -COOM _a , -COOR ⁵

T = -U ¹ - (CH (CH 3) -CH ₂ -O) _x - (CH ₂ -CH ₂ -O) ₇ -R ⁶

-WR ⁷

-CO- [NH- (CH ₂ ) ₃ ] _s -WR ⁷

-CO-O- (CH ₂ ) _Z -WR ⁷

- (CH ₂ ) _Z -V- (CH ₂ ) _Z -CH = CH-R ²

-COOR ⁵ in the case of S = -COOR ⁵ or COOM ₃ U ¹ = -CO-NH-, -O-, -CH ₂ O- U ² = -NH-CO-, -O-, -OCH ₂ - V = -O-CO-C ₆ H ₄ -CO-O - or -W-

R ⁴ = H, CH ₃

R ³ = aliphatic hydrocarbon radical having 3 to 20 carbon atoms, cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, aryl radical having 6 to 14 carbon atoms

R ⁶ = _R 2 _^ - [(CH ₂ ) ₃ - NH] ₃ - CO - C = CH

R ⁴ S

R ⁷ = R ² , - (CH ₂ ) _Z - O-CO-C = CH

R ⁴ S

r = 2 to 100 s = 1, 2 z = 0 to 4

X = 1 to 150 y = 0 to 15

mean as well

d) 0 to 47.9 mol groups of the general formula IVa and / or IVb included

-CH CH-CH CH

COO ₃ M COX ^ ^ ₅ .

O Y O

IVa IVb with the meaning given above for a, M, X and Y.

contains.

9. Dispersion according to claims 1 to 7, characterized in that the base of the copolymer

Oxyalkenylglykol alkenyl ether and the copolymer contains the following components:

a. 10 to 90 mol% of the groups of the formula IVa and / or IVb -CH CH-CH CH

COO ₃ M COX ^ ^C _{\ /} ⁰ ^.

O Y O

IVa IVb

in which

M = hydrogen, monovalent or divalent metal cation, ammonium ion, organic amine radical,

a = 1, or in the case where M is a divalent metal cation, is 1/2,

X = also -0M _a or

-0- (C _m H _2m O) _n - R ¹ with R ¹ = H, aliphatic hydrocarbon radical having 1 to 20 C atoms, cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, optionally substituted aryl radical having 6 to 14 C atoms,

m = 2 to 4,

n = 0 to 200,

-NHR ² and / or -NR ² ₂ with R ² = R ¹ or -CO-NH ₂ and Y = O, NR ² b) 1 to 89 mol% of the formula II

- CH ₂ - CR ^J -

(CH ₂ ) pO- (C _m H _2m O) _n -R ¹

VI

wherein R ³ = H, aliphatic hydrocarbon radical having 1 to 5 C atoms p = 0 to 3 and R ¹ , m, n have the abovementioned meaning and

c) 0.1 to 10 mol% of the groups of the formula IHa or IHb

R ⁴ R ² R ²

- CH - C - - CH - CH CH - CH -

ST (CH ₂ ) _Z V (CH ₂ ) _Z purple INb

in which

SS = -H, -COOM _a , -COOR ⁵

6

T = - U ¹ - (CH - CH ₂ - O) _x - (CH ₂ - CH ₂ - O) _y - R

CH

-WR ⁷

-CO- [NH- (CH ₂ ) 3] _s -WR ⁷

-CO-O- (CH ₂ ) _z -WR ⁷ - (CH ₂ ) _Z -V- (CH ₂ ) _Z -CH = CH-R ¹

-COOR ⁵ in the case of S = -COOR ⁵ or COOM ₃ U ¹ = -CO-NH-, -O-, -CH ₂ O- U ² = -NH-CO-, -O-, -OCH ₂ V = -O-CO-C ₆ H ₄ -CO-O- or -W- W =

R ⁴ = H, CH ₃

R ⁵ = aliphatic hydrocarbon radical having 3 to 20 C atoms, cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, aryl radical having 6 to 14 C atoms

R ⁷ = R ¹ , - (CH ₂ ; -O-CO-C = CH

R ^

r = 2 to 100;

s = 1, 2;

z = 0 to 4

x = 1 to 150;

y = 0 to 15.

10. Dispersion according to claims 1 to 7, characterized in that the base of the copolymer

Oxyalkenylglykol- (meth) acrylic acid ester and the copolymer contains the following components:

CH ₂ = C - R ¹

COO (R ² O) _m R ³ XV

wherein

R ^{1 represents} a hydrogen atom or the methyl group,

R ^{3 is} a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and

m is a value which is the average number of moles of oxyalkylene groups, where m is an integer in the range of 1 to 200.

95 to 2 wt .-% of a monomer of the (meth) acrylic acid type (b) of the general formula XVI

CH ₂ = C - R ⁴ XVI

COOM ¹

wherein

R ^{4 represents} a hydrogen atom or the methyl group, and M ^{1 represents} a hydrogen atom, a monovalent one Metal atom, a divalent metal atom, an ammonium group or an organic amine group,

and 0 to 50% by weight of another monomer (c) copolymerizable with these monomers, with the proviso that the total amount of (a), (b) and (c) is 100% by weight.

11. A process for the preparation of the dispersion according to claims 1 to 10, characterized in that one

a) with stirring to an aqueous starting dispersion of silica, in which the and / or agglomerates a mean diameter of less than 1 micron and a

BET surface area greater than 50 m ² / g, a flow agent in the form of a powder or as an aqueous solution of the flow agent and optionally further diluted with water

or

c) dispersing the silica powder in an aqueous phase, preferably in water, and then adding the resulting dispersion to an aqueous solution of the flow agent.

12. The method according to claim 11, characterized in that the flow agent is a polycarboxylate ether.

13. Use of the dispersion according to claims 1 to 10 as concrete admixture.

14. A cement-containing preparation containing the dispersion according to claims 1 to 10.

15. A cementitious preparation according to claim 14, characterized in that the concrete mixture contains 0.01 to 2% by weight of silica, based on cement.